Structural and Thermodynamic Variation in Nickel Aluminate Spinel

New structural and calorimetric data for samples of NiAl₂O₄ quenched from 600° to 1560°C are presented The spinel remains stoichiometric for all heat treatments. Based on the refinement of X-ray powder patterns, it is shown that the degree of disorder, defined as the mole fraction of tetrahedral sites occupied by Al³⁺, changes from x = 0.82 at 600°C to 0.78 at 1560°C. Simultaneously, the lattice parameter and enthalpy vary in a complex manner with quench temperature. The largest lattice parameter (0.80500 ± 0.00004 nm) and most exothermic enthalpy of annealing (heat released when sample is equilibrated at 780°C; -10.1 kJ/mol) occur for the sample quenched from 1100°C. A linear correlation exists between the heat of annealing and the lattice parameter. The results have been interpreted as a superposition of at least two effects: (1) the disordering of Ni²⁺ and Al³⁺ ions between octahedral (16d) and tetrahedral (8a) sites and (2) a second process, which may be a small amount of the disordering of ions into the usually empty (16c) sites.     

Mechanochemical Synthesis of Magnesium Aluminate Spinel Powder at Room Temperature

MgAl₂O₄ spinel was successfully synthesized using a mechanochemical route that avoided the formation and calcination of its precursors at high temperatures. The method involved a single step in which γ-Al₂O₃–MgO, AlO(OH)–MgO, and α-Al₂O₃–MgO mixtures were milled at room temperature under air atmosphere. The formation of MgAl₂O₄ occurred faster with γ-Al₂O₃ than with AlO(OH) or α-Al₂O₃. After 140 h, the mechanochemical treatment of the γ-Al₂O₃–MgO mixture yielded 99% of MgAl₂O₄.     

Deterioration in the Final-Stage Sintering of Magnesium Aluminate Spinel

Sintering of magnesium aluminate spinel of the MgO-excess, stoichiometric, and Al₂O₃-excess compositions has been investigated under vacuum and in air for the effect of low oxygen partial pressures. Densification enhancement of the surface layer is due to MgO evaporation which generates oxygen vacancies in the host crystal lattice. Regions of different grain sizes are observed from samples sintered under both conditions. Microstructural features of pairwise breakup of particle chains representing differential sintering are characteristic of the less-densified sample interior. The densification improved initially and yet was retarded in the intermediate sintering stage when the density exceeded 75% with vacuum-sintering owing to MgO evaporation.     

Hardness and Depth-Dependent Microstructure of Ion-Irradiated Magnesium Aluminate Spinel

Stoichiometric polycrystalline magnesium aluminate spinel has been irradiated at 25° and 650°C with 2.4-MeV Mg⁺ ions to a fluence of 1.4 × 10²¹ ions/m² (∼35 dpa (displacement per atom) peak damage level). Microindentation hardness measurements and transmission electron microscopy combined with energy dispersive X-ray spectroscopy measurements were used to characterize the irradiation effects. The room-temperature hardness of spinel increased by about 5% after irradiation at both temperatures. There was no evidence for amorphization at either irradiation temperatures. Interstitial-type dislocation loops lying on {110} and {111} planes with Burgers vectors along 〈110〉 were observed at intermediate depths (∼1 μm) along the ion range. The 〈110〉{111} loops are presumably formed from 〈111〉{111} loops as a result of a shear on the anion sublattice. Only about 0.05% of the calculated displacements were visible in the form of loops, which indicates that spinel has a high resistance to aggregate damage accumulation. The peak damage region contained a high density of dislocation tangles. There was no evidence for the formation of voids or vacancy loops. The specimen irradiated at 650°C was denuded of dislocation loops within ∼1 μm of the surface.     

Deformation Mechanism of Fine-Grained Magnesium Aluminate Spinel Prepared Using an Alkoxide Precursor

Polycrystalline MgAl₂O₄ spinel with high purity and stoichiometric composition was prepared using alkoxide precursors. The average grain size of the polycrystal was fine (1.7 μm). The deformation mechanism of the polycrystal was investigated in air at temperatures of 1300°–1400°C. At 1300°C, oxygen lattice diffusion controlled the deformation, despite the fine grain size; however, increases in the temperature and applied stress caused cavities to nucleate and grow. Spinel possessed better creep resistance than alumina of comparative grain size. The effective diffusion coefficient was determined as follows: [formula omitted]     

Preparation of Magnesium Aluminate Spinel Containing Controlled Amounts of 17O Isotope

Magnesium aluminate spinel (MgAl₂O₄) with an ¹⁷O enrichment (¹⁷O/O_Tot) of about 23 at.% was prepared by reacting fine mixtures of aluminum hydroxide (enriched with ¹⁷O) and magnesium oxide of normal isotopic content. The material was prepared for experiments in which the radiation damage produced in a fusion reactor is simulated by fission reactor exposures. The powder mixtures were obtained by hydrolyzing, with water containing the ¹⁷O iostope, a mixture of aluminum isopropoxide and magnesium oxide powder. The mixture was converted into pure spinel by a series of heat treatments and grindings. Essentially fully dense bodies, which contained about 45% of the ¹⁷O isotope initially present in the water, were successfully fabricated provided that all thermal treatments were conducted in argon or vacuum atmospheres.     

EXAFS Study of Cation Distribution in Nickel Aluminate Ferrites

A new method for analyzing the cation distribution of spinel crystals by extended X-ray absorption fine-structure spectroscopy has been developed to overcome the disadvantage of X-ray diffraction, which cannot readily distinguish among different transition-metal ions. EXAFS analysis was conducted on Ni²⁺ and Fe³⁺ ions in nickel aluminate ferrites, and the cation distributions obtained were in good agreement with values obtained by other methods. The ratio of tetrahedral sites occupied by Ni²⁺ ions decreases with increasing iron content. Fe³⁺ ions distribute nearly equally to both tetrahedral and octahedral sites. Apparently, not only crystal-field stabilization energy but also ion size affects cation distribution.     

Temperature Dependence of the Cation Distribution in Nickel Aluminate Spinel from Thermodynamics and X-Rays

The single crystal NiAl₂O₄ was prepared by a solid-state reaction. The change of its cation distribution with temperature was calculated by a modified thermodynamic equation by including a new parameter δ, which is a characteristic of nonconfiguration entropy. The calculated results showed that the degree of inversion for NiAl₂O₄ decreases with temperature, although the temperature dependence of cation distribution is very weak. This result was supported by X-ray diffraction measurement.     

Synthesis of Magnesium Aluminate Spinel Platelets from α-Alumina Platelet and Magnesium Sulfate Precursors

Spinel platelets were formed from a powder mixture of 3–5 μm wide and 0.2–0.5 μm thick α-Al₂O₃ and 1–8 μm (average 3 μm) MgSO₄ heated 2 h at 1200°C. The hexagonal platelet shape of the original α-Al₂O₃ platelet was maintained in the spinel, although their size was slightly increased and their surface roughened. When a mixture of α-Al₂O₃ platelets and MgO powder was heated 3 h at 1400°C, the spinel formed lost the platelet morphology of the alumina.     

Grain-Boundary Migration in Nonstoichiometric Solid Solutions of Magnesium Aluminate Spinel: I, Grain Growth Studies

The grain-boundary mobility in magnesium aluminate spinel (MgO · nAl₂O₃) of magnesia-rich ( n < 1) and alumina-rich ( n > 1) compositions has been measured from normal grain growth in dense, hot-pressed samples. Over the temperature range 1200° to 1800°C, the mobility in magnesia-rich compositions is found to be greater than that in alumina-rich compositions by a factor of 10² to 10³. Within the alumina-rich field, the mobility varies by less than a factor of 10 over the composition range 1 > n > 1.56. Nearly stoichiometric spinels (1 < n < 1.07) form a variety of sources and starting materials exhibit boundary mobilities within a factor of 5 at fixed temperature, showing an impurity tolerance which has not been found in other ionic solids.     

Synthesis of Zinc Aluminate Spinel Film through the Solid-Phase Reaction between Zinc Oxide Film and α-Alumina Substrate

We synthesized spinel ZnAl₂O₄ film on α-Al₂O₃ substrate using a solid-phase reaction between the pulsed-laser-deposited ZnO film and α-Al₂O₃ substrate. Auger electron spectroscopy showed that the atomic distribution in the spinel ZnAl₂O₄ was inhomogeneous, which indicated that the reaction was diffusion controlled. Based on X-ray fluorescence measurements, the apparent growth activation energy of ZnAl₂O₄ was determined as 504 kJ/mol. X-ray diffractometry spectra showed that, as the growth temperature increased, the ZnAl₂O₄ film became disoriented from the single (111) orientation. The ZnAl₂O₄ (333) diffraction peak shifted toward a small angle, and its full-width at half-maximum decreased from 1.30° to 0.37°. At the growth temperature of 1100°C, the morphology of the ZnAl₂O₄ was initially transformed from islands to stick structures, then to bulgy-line structures with increased growth time. X-ray diffractometry spectra showed that these transformations were correlated with changes of ZnAl₂O₄ orientation.     

Grain-Boundary Migration in Nonstoichiometric Solid Solutions of Magnesium Aluminate Spinel: II, Effects of Grain-Boundary Nonstoichiometry

The grain-boundary chemistry of magnesium aluminate spinel solid solutions MgO· n Al₂O₃ in which grain growth measurements were reported in part I has been investigated in order to understand the mechanism of grain-boundary migration. It is found that although segregation of impurity Ca and Si is common, much larger deviations in grain-boundary stoichiometry are present. There is an excess of Al and O relative to Mg at grain boundaries in all compositions. Grain-boundary migration appears to be rate-limited by solute drag from intrinsic defects accommodating lattice nonstoichiometry, rather than by extrinsic solutes, consistent with the observed impurity tolerance of grain-boundary mobility. Different rate-limiting defects are proposed for magnesia-rich and alumina-rich spinels.     

Effect of Controlling Parameters on the Reaction Sequences of Formation of Nitrogen-Containing Magnesium Aluminate Spinel from MgO, Al2O3, and AlN

The reaction sequences of the formation of nitrogen-containing magnesium aluminate spinel from MgO, Al₂O₃, and AlN were investigated as a function of temperature through dilatometric study and as a function of time through isothermal heat treatments. The natures of reactions are described through the appearance of phases in conjunction with densification behavior and the change in lattice parameter of the spinel phase. Although the dilatometric study provides the detail insights of the formation sequence, the isothermal runs reveal new information about the differential rate of reactivity of the reacting species that suggested a tentative controlling mechanism. Through the initial formation of magnesium aluminate, oxygen-rich solid solution (MgAlON) forms, which ultimately reacts with the rest of AlN to reach its nominal composition. Nitrogen diffusion through MgAlON lattice seems to be rate controlling.     

Epitactic Nucleation of Spinel in Aluminosilicate Gels and Its Effect on Mullite Crystallization

Control over the structure of hybrid (colloidal + molecular) aluminosilicate gels was utilized to demonstrate that precursor chemistry has a direct and controllable effect on the ∼1000°C crystallization of spinel and mullite in molecular precursor systems. Synthesis or preparation conditions leading to the development of a cubic, transition alumina result in the epitactic nucleation of spinel at ∼1000°C in gels that otherwise crystallize directly to mullite at ∼1000°C. Thus, the preference for spinel nucleation in gels derived from solution precursor systems whose chemistries promote formation of transition alumina readily explains the reported inability to obtain substantial mullite yields at ∼1000°C. Isothermal transformation kinetics of colloidal and hybrid gels show that in the absence of direct mullite formation at ∼1000°C, the release of alumina from the spinel-type crystal structure becomes the rate-controlling step in the transformation. This necessitates higher temperatures for mullite formation and limits the kinetic enhancement possible with extrinsic increases in mullite nucleation frequency.     

TiO2对电熔合成镁铝尖晶石的影响

以轻烧氧化镁粉、工业氧化铝为原料合成电熔镁铝尖晶石材料,重点研究二氧化钛为添加剂对电熔合成镁铝尖晶石的物相组成,显微结构的影响,通过XRD,SEM分析试样的物相组成、晶胞参数和断口的微观形貌.研究发现:二氧化钛为外加剂可以增大镁铝尖晶石的晶胞参数、提高材料的体积密度进而改善材料的烧结性能,并且随着二氧化钛加入量的增加镁铝尖晶石的晶胞参数和晶胞体积呈现先增大后减小的变化规律.分析认为由于二氧化钛、钛酸镁固溶到镁铝尖晶石中促使镁铝尖晶石的晶胞参数和晶胞体积增大,而过量的钛酸镁位于晶界阻碍镁铝尖晶石的长大,导致镁铝尖晶石的晶胞参数和晶胞体积减小.在电熔法制备镁铝尖晶石时,二氧化钛的加入量不宜超过5wt%.     

铝镁尖晶石对镁质浇注料性能的影响

针对镁质浇注料在使用过程中抗渣渗透能力差,易剥落等问题,本实验加入铝镁尖晶石对镁质浇注料进行改性研究.实验分为两部分:先将镁砂细粉、镁质添加剂和铝镁尖晶石细粉等机压成型,进行高温热处理,研究其物相组成和显微结构;然后以电熔镁砂为骨料,电熔镁砂细粉、氧化铝微粉、铝镁尖晶石细粉和镁质添加剂为基质,按骨料:细粉=75∶25进行配制,研究铝镁尖晶石加入量对镁质浇注料性能的影响.结果表明:在镁质材料中引入尖晶石,能促进结构致密化;加入9％的铝镁尖晶石的浇注料试样显气孔率低,线变化率小,体积密度大,强度大,抗渣性能最好,由于镁铝尖晶石生成时体积膨胀,使得材料结构致密化;同时能有效吸收渣中CaO及FeOx等成分,减少渣的渗透作用,从而提高了浇注料的抗渣性能.     

Preparation of ZnGa2O4 Spinel Fine Particles by the Hydrothermal Method

ZnGa₂O₄ fine particles with a single phase of spinel were synthesized from a mixed solution of gallium sulfate and zinc sulfate in the presence of aqueous ammonia under hydrothermal conditions above 180°C. The effects of treatment temperature and ZnO/Ga₂O₃ molar ratio in the starting solution on the crystallite size, morphology, lattice parameter, and chemical composition of the ZnGa₂O₄ spinel particles were examined. Spinel with different morphologies, cubic nanoparticles, and elongated rodlike particles were thought to be formed based on the structure of amorphous gallium hydroxide and needlelike GaO(OH) particles, respectively. By treatment at a higher temperature, these particles with nonstoichiometric composition grew large and thick, and their composition approached ZnO/Ga₂O₃= 1. With an increase in the starting ZnO/Ga₂O₃ molar ratio, the lattice parameter of the synthesized ZnGa₂O₄ spinel approached the reported value for the stoichiometric composition and reached a = 0.8335 nm at ZnO/Ga₂O₃= 1.95 by treatment at 240°C for 50 h.     

镍铝尖晶石基铝用惰性阳极导电性的初步研究

以减轻惰性阳极材料对铝液的污染为目的 ,选用NiAl2 O4合成尖晶石作为陶瓷相 ,加入金属铜、镍以提高材料的导电性 ,采用粉末冶金的方法制备金属陶瓷型铝用惰性阳极。对惰性阳极试样的一些理化指标进行了测定 ,着重研究了试样的电导率随温度变化的规律。在试样制备条件一般、烧成试样气孔率较高的情况下 ,试样的电导率达到 2S·m-1,电导率还有进一步提高的空间     

Thermal Expansion Characteristics of Alumina–Magnesia and Alumina–Spinel Castables in the Temperature Range 800°–1650°C

The thermal expansion of Al₂O₃–MgO castables containing 5.5 wt% MgO and 1.36 wt% CaO and Al₂O₃–spinel castables containing 20 wt% spinel having 95 wt% Al₂O₃ and 1.7 wt% CaO was measured in the temperature range of 800–1650°C by dilatometry. A sharp increase in expansion from around 1425° to 1525°C, followed by a sharp decrease with further increasing temperature, is characteristic of Al₂O₃–MgO castables. The sharp increase in expansion is believed to be caused by the bond linkage between the CA₆ and spinel grains in the bonding matrix, while the sharp decrease is apparently related to liquid-phase sintering. The sharp increase and decrease in expansion were not observed in Al₂O₃–spinel castables because of the much lower MgO (around 1 wt% MgO) and impurity contents. The magnitude of thermal expansion of calcium aluminate bonded castables containing self-forming or preforming spinels or both is dictated by the MgO content of the castables.